Method for producing unsaturated hydrocarbons



Oct. 7, 1952 D. R. BLUMER 2,613,233

METHOD FDR PRoDucING UNSATURATED HYDRocARBoNs l Filed Dec. 28, 1948 2 SHEETS- SHEET 1 Oct. 7, 1952 D. R. BLUMER METHOD FOR PRoDucING-UNSATURATED HYDRocARBoNs Filed'neo. 2a, 1948 2 Sl-IEETS-S-EET 2 aok/Nolmvad Patented Oct. 7, 1952 METHOD FOR PRODUCING UNSATURATED f HYDRocARBoNs Donald R. Blumen. st. Paul, Minn., assigner to yPhillips Petroleum Company, a lcorporation of Delaware Application December 2s, 194s, serial No'. 67,673

t 15 claims. (ci. 26o-677) This invention relates to a process for the pro duction of unsaturated hydrocarbons from diisopropyl. In one of its aspects this invention relates to the production of mono-olenic hydrocarbon derivatives of diisopropyl by the chlorination of diisopropyl and dehydrochlorination of the chlorinated products. This invention is useful for the production of tetrarnethylethylene by the chlorination ofdiisopropyl and dehydrochlorination of the monochlorides thus produced.

Mono-olenic hydrocarbon derivatives of diisopropyl, such as tetramethylethylene, are valuable compounds for the production of higher-boiling hydrocarbons and especially those hydrocarbons that are highly desirable in gasoline. For.. example, tetramethylethylene may be methylated to produce triptane which is a highly valuable hydrocarbon. Thus the value of producing these mono-olenic derivatives of diisopropyl is quite readily apparent.

It is an object of this invention to produce mono-olenic hydrocarbon derivatives of diisopropyl.

'Y It is another object of this invention to lproduce tetramethylethylene.

"Another object of this invention is to produce valuable unsaturated derivatives vof diisopropyl by the chlorination of diisopropyl and dehydrochlorination of the monochlorides thus produced.

A further objectof this invention is to provide a novel process for the production of tetramethylethylene which involves chlorination of diisopropyl, dehydrochlorination of the resulting monochlorides and isomerization of the byproduct olenic hydrocarbons to the desire product.

y A further object of this invention is to provide l a novel process for the production of tetramethylethylene which involves chlorination of diisopropyl, separating the tertiary chloride derivative from the primary chloride derivative, dehydrochlorinating each chlorinated derivative anda isomerizing the by-product oleflns to the desired product. i

, Further and additional objects of'my invention will be apparent from the description hereinbe-` r drawings, 2,3-dimethylbutane, which is ordinarily referred to as diisopropyl or DIP in this specification, is introduced into line l, wherein it is joined by the diisopropyl distillate from fractionator "l, which is introduced via line l2 and pump IZA. It is ordinarily desirable to use vdiisopropyl of 98 per cent purity or better as the charge into line l. However, diisopropyl of lower purity may be used; it may be as low as 90 per cent purity or lower, but these lower purities require additional fractionation steps in the chlorination-dehydrochlorination system in order to remove methylpentanes and other impurities from the diisopropyl recycled to the chlorinae' tion step, to'remove. chlorination products ,of these impurities from the diisopropyl chlorides, and to separate olen impuritiesresulting therefrom from the dehydrochlorination products. The combined diisopropyl stream is passed through preheater 2 wherein it is heated to a temperature approaching its boiling point, preferably in the range of 40 to 55 C., before it is passed into chlorinator 4 through line 3 and check valve 3A which serves to prevent chlorine from 1backing up into the hydrocarbon line. Chlorine is added to the chlorinator via line 5 into headers nwhich serve toqeffect multipoint addition of the chlorine to the hydrocarbon. The chlorinator is preferably packed with broken refractory, glass, or other material inert Vto the action of chlorine, which serves to give ,good dispersion ofthe chlorine and hydrocarbon flowing through the frea'ctor and to prevent explosive pockets from forming therein. The hydrocarbon to chlorine molar ratio is ordinarily maintained within the range of 8:1 to 10: 1 so that 95 per cent or more of the diisopropyl chlorinated isconverted `to the moncchlorides. With ahydrocarbontochlorine ratio within the range of 4:1r to 5:1 at thepoint of introduction vof the chlorine, the Vfinal chlorinated productsrcontain approximately 90 and 10 mole per cent of the diisopropyl monoand dichlorides, respectively. With lower ratiosv than thisprogressively more diand-tri'- chlorides are formed." Ordinarily, of themcno: chlorides produced, about BO'to 35 per cent by weight isthe teritary derivative and about 65.*to -7'0 per cent by weight is the primary derivative.

Because-of the fact that theV diisopropyl enters chlorinator 4 below its boiling point, substantiallyV all of the heat ofthe chlorination reaction is absorbed by the excess diisopropyl as heat of vaporization, thereby preventing the reaction temperature from rising `dangerously "and getting 'i into the explosive range.' `Under these operating 0f my invention, and I do not intend 'tolimit my process to any one particular method.

The efuent from the chlorinator is passed via line 6 into fractionatorl'ifiwhereinxthei chlorides of diisopropyl are separated as the kettle product and the diisopropyl is condensed outv as the overhead product.

Hydrogen chloride, 'a

small amount of diisopropyl and traces of unl reacted chlorine pass overhead as vapors from Afractionator I via linelandcondenser 8A whereiniV the. greaterk part'.` offthe diisopropyl and traces of Yitschlorides arecondensed. rhis condensate ows intorefluxreceiven from which Areflux is returned through line I.I. to fractionatorl. The hydrogen kchloride eiuent containing traces of unreacted .chlorineA andY small amountsfof diisopropyl vaporpasses fromreuxreceiver 9 vialine l0 from which it ordinarily ispassed into an cil scrubber. (not shown) for. separation and recovery of the relatively-smallamounts of diisopropyl vapors contained therein. The. product portion of the diisopropyl which is takenofi from reflux receiver-9 through line I2 andrecyclepump |2A is returnedito' chlorinator. 4 for further processing, and reiiuxis charged via linel I to-fractionator 1. The diisopropyl chloride Lproductscontaining a smallamount of diisopropyl are takenV off from fractionator 1 asthe kettle product through line 13- .into Yvacuum fractionator .,I. Ordinarily, fractionator 1 isY operated at a kettle temperature of 85r to. 100i C., and notfmuch in excess thereof by. taking off sufficientdiisopropyl with `the chloride derivatives. to `keep .-the temperature within the desired range vin order to. avoid dehydrochlorination in this column.v l l.

In` vacuum fractionator i4 theresidual diisopropyl-isstripped off lunder vacuum. A cut ofthe mixed.diisopropylmonochlorides is-.takenv off, and the diisopropyl chlorides higher than the monoderivativeare removed as kettleproduct. It is advantageous to operate-this column at'an absolutevpressure of about 5.5 to 6.0.in'ches of mercury or less so Athat the kettletemperature will not exceed 1GO-to 110C. Then the diisopropyl monochloridesare taken-off at a temperatureapproximately in the range of 55. to 75 C., and appreciable dehydrochlorination during this-separation step is avoided. Under these' conditions the boiling point-ofdiisopropyl is-so low that, unless refrigeration is used in condenser l5, most of the diisopropyl Will'flash over via line I6 and fmay be recovered from the vacuum ejector oli-pumpl effluent by condensation or oil scrubbing. With refrigeration, much ofthe diisopropyl is withdrawn vialine l1 and pump IIA. If ldesired. the diisopropyl from linesr Iiand Ilmay be recycledto line i. The fraction of mixed diisopropyl monochlorides is withdrawn via line I8 and pump ISA and introducedinto fractionator-dehydrochlorinator which is operated at about atmospheric pressure. The higher chlorides of diisopropyl are withdrawn vialine 1 9, and pump I'SA and may be used forl the production of 2,3.-dimethylbutadiene-1,3v and other valuable products.

` "Selectivedehydrcchlorination of the tertiary diisopropyl monochloride (B. P.=112 C.) is effected by reuxing it in the presence of the higher boiling primary monochloride (B. P.=122 C.) in the fractionator-dehydrochlorinator 20 at about atmospheric pressure, the kettle temperature ordinarily being inftherange of to 130 C. This reactor may be .packed with refractory, stainless steel, or other suitable rings, saddles, or like packing material. It is advantageous in many cases that thev refractory packing be impregnated with small amounts of dehydrochlo- "rinati'oh catalyst such as barium chloride, bismuthv chloride, or the like in order to accelerate the dehydrochlorination of the tertiary monochloride. Othercatalysts which may be used for lthis-purpose are: ferro-molybdenum, phosphoriron, ferro-manganese, ferro-chrome, ferro-aluminum, nickel-aluminum and the like, wherein the bimetallic couple effect is advantageous in effecting gdehydrochlorination. The rare metals such as platinum, palladium, ruthenium, and the like in nely divided state and used in a small quantity on a suitable support such as pumice, kieselguhr (diatomaceous earth), Floridin, or the like are also very leffective dehydrochlorination catalysts for useY in this fractionator-dehydrochlorinator. The greater part of the` dehydrochlorination eiiiuent consisting principally of 2,3- dimethyl-Z-butene andsmaller concentrations of 2,3-dimethyl-1-butene and 3,3-dimethyl-1-butene and the hydrogen chloride resulting from the dehydrochlorination reaction, passes out of the column at a temperature which is ordinarily in the range of 50 to 100 C. via line 2| into the quencher-fractionator 28, wherein a separation is effected. A portion of this effluent is withdrawn from line 2l through line 22'and condenser 22A into reilux receiver 23 from which any desired part of the hydrogen chloride in theeiiluent can be vented via line 24 or any desired part of it may be recycled via lines 25 and I8 into fractionatordehydrochlorinator 20 Where it serves asa catalyst activator or as a catalyst-for the dehydrochlorination reaction. It is in some cases desirable to add traces of moisture or of organic peroxides activated lby still smaller amounts of quinone or organic acids at thispoint tofserve as catalysts or promoters for the dehydrochlorination-reaction. The condensate from receiver 23 is returned via line 26 to fractionator-dehydrochlorinator 20 as reflux. The 1chloro-2,3- dimethylbutane remaining after the selective dehydrochlorination step is Withdrawn from fractionator-dehydrochlorinator 20 via line 21 into storage reservoir 38.

To the olefin-hydrogen chloride stream entering quencher-fractionator 28 via line 2l is added a diluent which is non-reactive with hydrogen chloride-and which is ordinarily lower-boiling than the lowest boiling hexene isomer, 3,3-dimethyl-l-butene (B. P.=41.2 C.) and easily separable therefrom by fractionation. Normal pentane (B. P.:36.0 C.) serves this vpurpose satisfactorily; however, operation of vthis separation process'is not limited to theuse thereof, and other inert diluents may be used. The normal pentane or other diluent dilutes the eiiiuent stream in line 2l, causing less intimate contact ofthe oleiins with the hydrogen chloride, and vaporization of the inert diluent in addition tends to sweep the hydrogen chloride out of contact with the olen-rich liquid phase, thereby-retarding back-reaction of the olen with the hydrogen chloride. In quencher-fractionator 28 the n-pentane and hydrogen chloride are rapidly swept overhead 'where they Vcontact, condenser '29" 'which serves to return part of the n-pentane `asfr'eiiux to the column and allows the remaining-npentane and hydrogen .chloride to pass overhead throughline 3B. This eiliuent is subsequently 'put through an oil absorber (not shown) to recover the n-pentane for reuse in the process. The liquid n-pentane separated in the column is taken off via line 3|. The recovered and make-up n-pentane are added via vline-32 and pass with the n-pentane in line 33 'to line' 2|.. The 3,3-dimethyl-1-butene (B. P.: 41.2. C.)' is taken off from fractionator 28 via line,34, the 2,3-dimethyl-1-butene (B. P.: 55.6 C.) Vvia line 35, the 2,3-dimethyl-2-butene -(B. 11.173.2-o C.) via line 35, and conducted to storage, `not shown. The small amount of tertiary. 1 .diisopropyl `monochlorde which ris formed by recombination of `hydrogen chloride with -the above 2,3-.dimethylbutene isomers is withdrawn via line 31 and recycled to fractionator-dehydrochlorinator 20.

`.The low` boiling hexene isomers which are Widthdrawn from quencher-fractionator 28 via lines 34 and 35 are passed via line 51 and line 59 into catalytic isomerizer El)y which is 'preferably constructed as affractionator, the packing of Awhich may .beV the isomerization catalyst or suitable refractory or other column packing impregnated with the catalyst. Catalysts which are suitable for this purpose are Floridin, kaolin, diatomaceous earth, bauxite. activated alumina, silica gel, or the like, or the same materials or inert support material such as pumice, impregnated with a slight amount of acid, such as sulfuric or phosphoric, or with acidic sulfate, phosphate, fluoride, or like salts of the alkali, alkaline earth.'v or other inorganic elements. In this isomerizer, which is preferably operated at total reflux, the vaporsare condensedy and returned as reilux` by means of a cooling coil, The lowv boiling hexene isomers are catalytically rrearranged to 2,3-dimethyl-Z-butene and thereby pass ydown the column and are withdrawn through line 52. They may be conducted to storage (not shown) or admixed with the products `in lines 36 and 53, and any highboiling polymers whichA are formed are withdrawn as kettle residue via line 63. i

The 1-chloro-Z,3-dimethylbutane from selective dehydrochlorination` fractionator 2t passes ,from storage reservoir 38 via line 39 intowline 40 along with the recycle from quencher-fractionator which passes via line 54, recycle pump 55, and line 56 into line 40. Via line 45 the stream flows into preheater 4| and via line 42 intoV catalytic dehydrochlorinator 43 wherein substantial dehydrochlorination of the primary diisopropyl monochlorde is effected. Catalysts such as were cited for use in reactor `2l) may be' used herein also.V The hot dehydrochlorination effluent passesfthrough line 44, and n-pentane or other suitable quenching material is added through line before the cooled ef- -fluent passes into quencher-fractionator 45 wherein part of the n-pentane is condensed and returned as reux by the cooling coil 46.- Hydrogen chloride and uncondensedy yn-pentane vapors pass overhead through line 41.to an oil scrubber `(not shown) wherein the n-pentane is recoveredfby absorbing it in the oil and subsequently flashing it off from the oil. N-pentane or other suitable inert diluent is taken off from column ..45 via4 line.48 and make-up Vdiluentlis added via line- 49." The ;npentane Vthen passes via lline 50 into the stream in line 44. The lower boiling hexene isomers, 3,3-dimethyl-1-butene and 2,3-dimethyl-1-butene are withdrawn from the column through lines 5l and 52, respectively. The 2,3-dimethyl-2-butene is withdrawn through line 53. The undehydrochlorinated 1- chloro-2,3dirnethylbutane residue and a small amount of 2-chloro-2,3-dimethylbutane, which is formed by recombination of hydrogen chloride with the 2,3-dimethylbutene isomers or lby rearrangement of the l-chloro derivative, leaves quencher-fractionator 45 via line 54 and is recycled by pump 55 and line 55. It is advantageous in many cases to subject the liquid passing via line 54 to additional fractionation in order to separate the small amounts of high boiling olefin polymers and highly chlorinated coml-butene and 2,3-dimethyl-1-butene, which are` taken off through line 5l and 52, respectively, are recycled through line 58 and line 59 to the catalytic isomerizer 60, which has been previously described wherein they are convertedto 2,3- dimethyl-Z-butene.

In the dehydrochlorination of the l-chloro-2,3 dimethylbutane, which is effected in catalytic dehydrochlorinator 43, much more rigorousoperating conditions are required than were necessary for the selective dehydrochlorination of the 2- chloro-2,3-dirnethylbutane in fractionator-dehydrochlorinator 2li. Preliminary thermal dehydrochlorination experiments with the primary diisopropyl monochlorde in a Pyrex reactor indicated that a temperature of 50G-600 C. (932- l112 F.) is required for any significant per pass conversion. In one thermal dehydrochlorination experiment at 609 C. (1128 F.) with a contact time of eight seconds and a mixed monochlorde charge containing 95 per cent by weight of the primary derivative a per pass conversion of 79 per cent was attained. An ultimate yield of 64 per cent of theoretical to the two useful 2,3-dimethylbutene isomers, of which about per cent .by weight was the l-oleiin, and 36 per cent of theoretical to undesired secondary reaction products was obtained.

Because of the relatively high temperature level required for thermal dehydrochlorination of the primary diisopropyl monochlorde and the production of appreciable amounts of waste secondary reaction products, catalytic dehydrochlorination was investigated to see if more satisfactory results could be obtained. A series of ten small scale experiments was made to determine the effectiveness of four catalysts for the dehydrochlorination reaction. Arranged in the order of decreasing initial catalytic activity under comparable experimental conditions these catalysts are as follows: steel turnings, bauxite of low iron content, anhydrous barium chloride, and 18 per cent chromium-8 per cent nickel stainless steel turnings. The steel and the less active stainless steel catalysts rapidly lost their activity with the formation of a llm on the surface of the catalyst, although the stainless steel retained its activity better than ordinary steel. The bauxite retained its catalytic activity well but promoted the formation of low-boiling decomposition products and high-boiling polymers. The anhydrous barium chloride produced the highest ultimate yields and did not lose its activity in the experiments. Experimental `data for representative -dehydrochlorination experiments with the primary diisopropyl monochloride using the barium chloride catalyst are presented in Example 4 hereinbelow.

By passing a mixture of diisopropyl monochlorides containing 97 to 98 per cent by weight of the primary derivative through catalytic dehydrochlorinator 43, containing puinice impregnated with about 10 per cent Iby weight of anhydrous barium chloride at 520 to 530 C. (968 to 986" F.) and at a space velocity of 0.2 liquid volumes of feed `per volume of catalyst per hour and by quenching the eiiluent `with n-pentane in quencher-fractionator It5, a per pass conversion to tetramethylethylene of 60 to 65 per cent and an ultimate yield of 98 to 99 per cent of the theoretical is attained. The olen product contains a few per cent of 3,3-dimethyl-1-butene; about a third is 2,3-dimethyl-1-butene; the remainder is 2,3-dimethyl-2-butene. Upon isomerization of the rst two hexene isomers to 2,3-dimethyl--butene in. catalytic isomerizer 0.0, the ultimate conversion to the latter olen is approximately 95 per cent or better.

Alternatively, in the reaction system illustrated in Figure 1, instead of passing the dehydrochlorination eluents from dehydrochlorinators 20 and 43 into quencher-fractionators 28 and 45, these effluents may be scrubbed concurrently or countercurrently with 1-ch1oro-2,3-dimethylbutane at a temperature such that substantially all of the 2,3-dimethylbutene isomers are retained in solution. but substantially all of the hydrogen chloride passes through undissolved. A temperature in the range of 35 to 50 C. is ordinarily satisfactory for this purpose. Under these conditions, the 3,3-dhnethyl-1-butene isomer which is produced in a relatively small amount is largely swept out with the hydrogen chloride, and it may be separated therefrom by scrubbing preferably with cold 1-chloro-2,3-dimethylbutane or with oil. Subsequently, the solution of olens in the scrubbing liquid is subjected to fractionation to recover the olefins. In those cases in which appreciable back reaction of the oleiins .with hydrogen chloride occurs to form the tertiary diisopropyl monochloride and the primary diisopropyl monochloride is used as the scrubbing liquid, it is desirable to recycle part of this scrubbing liquid to fractionator-dehydrochlorinator 20 to selectively dehydrochlorinate the tertiary monochloride formed. A compensatingy amount of the primary diisopropyl monochloride from this reactor is then recycled back to the scrubbing step as make-up.

Figure 2 is a diagrammatic drawing of this alternative method of operation. According to this drawing the effluents from dehydrochlorinators 20 and 43, as shown on Figure 1, pass via lines 2| and 44 respectively to scrubber |00. 1chloro 2,3-dimethylbutane passes from storage 38 via lines and |02 to scrubber |00 wherein it passes concurrently with the effluents from dehydrochlorinator 20 and 43. Scrubber |00 is operated at a temperature of 35 to 50 C., and the scrubbing liquid, 1-chloro-2,3dimethylbutane, leaves the scrubber via line |03 containing the 2,3-dimethylbutene isomers in solution. Hydrogen chloride and 3,3-dimethyl-1-butene pass from from scrubber |00 via line |04 to scrubber |05. Scrubber |05 is operated at a temperature lower than that o scrubber |00 and within the range of to 25 C. 1-chloro-2,3dimethylbutane passes from storage 38 via lines |0| and |06 to scrubber |05 where it is used as the scrubbing liquid. l At the low temperaturein scrubber |05 the hydrogen chloride is separated from the olen, and the hydrogen chloride leaves scrubber |05 via line |01. The scrubbing liquid containing 3,3-dimethyl-l-butene from scrubber |05 passes via line |08, and the scrubbing liquid and olens in lines |03 and |08 are combined for passage via line |09 to fractionator ||0. From fractionator ||0 tetramethylethylene is withdrawn via line I and 2,3-dimethyl-l-butene and .EL3-dimethyl,- l-butene are withdrawnvia lines ||2 and ||3 respectively. These latter olens are conveyed via line ||4 to an isomerization unit, as described in Figure 1, for conversionv to tetramethylethylene. scrubbing liquid is withdrawn from fractionator I0 via line ||5 for return to storage 30.

In another alternative embodiment. of the 1nvention quencher-fractionator 45 can be eliminated from thev process, and then the effluent from dehydrochlorinator 43 passes via lines 44A and 2| to quencher-fractionator 28 wherein said effluent is treated in the. same manner as and along with the eiiiuent from dehydrochlorinator 20, in a manner described hereinabove. In this method of operation 1chloro2,3-dimethylbutane in addition to the tertiary diisopropyl monochloride will pass from fractionator 28 to dehydrochlorinator 20 via line 31, and the l-chlorc-2,3 dimethylbutane leaves dehydrochlorinator 20, as previously described, via line 21 for passage to storage 30. Y

The following specific examples are exemplary of my invention.

Example 1 In a preliminary fractionation which was carried out to separate the primary and tertiary diisopropyl monochloride isomers from a monochloride fraction which resulted from the peroxide catalyzed chlorination of diisopropyl with sulfuryl chloride, it was observed that the tertiary monochloride dehydrochlorinated selectively leaving the primary derivative substantially undehydrochlorinated. This fraction, amounting to '79 grams (88 mL), which had been previously separated from the chlorination products by means of a one-plate vacuum distillation Vat a pressure in the range of 7.5 to 9.2 cm. of mercury and at an overhead temperature invv the range of 40.5 to 67.5 C. had a corrected boiling range of 102 to 138 C. at '760 mm. mercury, indicating that it contained a slight aomunt of the dlchlorides as well as a'small amount ofI lower boilingmaterial. This product was washed with water and dried with calcium chloride prior to redistilling the 73 grams of purified product at atmospheric pressure ina small column, which was packed with 35 inch diameter stainless -steel Fenske rings, and which was provided with a water cooled reilux head. During the first distillation, the overhead temperature was 49 C. initially, went up to C., and fell back to 111 C., while the corresponding kettle temperatures were 103, and 299' C., respectively. Considerable hydrogen chloride was evolved with the distillate during the early part of the distillation, but it practically ceased toward theend of the distillation while the primary diisopropyl monochloride was distilling. The dehydrochlorination which was effected in the distillation was catalyzed by the stainless steel packing andA the nickel and chromium chlorides formed on the surface thereof.

On redistilling the above distillate, 2,3-dimethyl-l-butene and 2,3-dimethyl-2-butene were separated before dehydrochlorination of the y primary derivative.

, '9 higher;boling `kettle products :recommenced at a kettle temperature of'about118 C.- By redistilling the olen-diisopropyl monochloride residue fractions twice more and combining and redstilling the kettle residue'fractions, the original productwas'separated into fractions which were principally tetramethylethylene and its isomers and a residue of primary diisopropyl monochloride. l Redistillation of the olen fraction indicated that it contained a trace of EL3-dimethyl- 1-butene and approximately ten volume per cent of 2,3-dimethyl-1-butene. 'Bromine numbers which were run on the lfractions recovered indichill the eiliuent with ice traps in order to obtain complete recovery of the'oleflns.

` Example 2 Inan experiment designed to prepare'pure primary and tertiary diisopropyl monochloride fractions" for use'in the determinationof the physical properties and investigation of the dehydrochlorination of the pure compounds,V a composite fraction rich in the monochlorides of diisopropyl was refractionated in all-glass apparatus at reducedpressure, which was in the range of 5.3 to 5.7 inches of mercury absolute pressure. The fractionation column, which was four feet long and had an internal diameter of one-half inch, was packed for a length of approximately forty-four inches with one-eighth inch diameter Pyrex helices. In this refractionation, which was carried out with a high reflux ratio,feven at the low overhead temperaturel in therange of about'31 to 69 C., 48grams o f tetramethylethylene were formed and recovered from the initial charge, representing a'dehy'd'rochlorination of l per cent by weight ofV the initial charge or 29 per centby Weight of the tertiary monochloride content of the charge. From this refractionation and corrections made for dehydrochlorination, it was determined that of the combined monochlorides charged tothe distillation, 34 per cent by weight was the tertiary derivative and 66 percent by weight was the Of the total charge to the column, 4 per cent by weight was the dichlorides of diisopropyl, which had not been removed .in the preceding fractionations.

Example 3. f

overhead temperature'wasjin the range of 50 to 80j C. andthe` kettle temperature in the lnge' of 120 to 130 C. The olefin product was prin-g cipally 2,3-dimethyl-2-butene, but it contained 15 to 25 per cent of 2,3-dimethyl-1-butene and a few per cent of 3,3-dimethyl-1-butene. These olens were separated in quencher-fractionator 28, and the two lower boiling isomers were sent to the catalytic isomerizer 6U for rearrangement to 2,3-dimethyl-2-butene. The over-all conversion of the tertiary diisopropyl monochloride to the latter olefin by these combined processes was 95 per cent of theoretical. v

Example 4 In Yone representative. experiment in which mixed diisopropyl inonochlorides,containing 95' per cent by weight ,ofthe primary derivative Were passed over anhydrous barium chloride (prepared'by dehydration of the dihydrate salt at 200 C. overnight) at 522 C vand rat a space velocity of 0.2 liquid volumes of monochlorides per volume of catalyst per hour and in which the effluent rwas quenched with ice Water and the dehydrochlorination eiuent was analyzed by fractionation, a per passconversion of approximately 60 per cent to olens, and an ultimate yield Yof 99 percent of theoretical, was attained. lThe, olen product was 39 per cent by weight 2,3- dimethyl-l-butene and 61 per centby weight 2,3-, dimethyl-Z-butene.

In a secondrurr made underl conditions comparable with the above, but with a charge containing 96 per cent by weight of primary diisopropyl monochloride and 4 per cent by weight ofl the diisopropyl dichlorides, `a per pass conversion of approximately per cent to the desired olefins was attained..A y Y In a third run made undersimilar conditions using a charge of mixed diisopropyl monochlorides containing 39 per cent by weight of the ter-pV tiary derivative, the per pass conversion was, slightly .less than half that attained with the preceding charge. Y l

These differences may have resulted from pos',- sibledifierences in activity of the catalysts used in the three experiments and from selective recombination of the hydrogen chloride with the olen isomers in the effluent at the quenching temperature of 0 C. which was used. Ithas been found ythat 2,3-dimethyl-2-butene reacts much morel rapidly With hydrogen chloride at ice temperature thanY does either 2,3-dimethyl-v 1butene or 3,3-dimethyll.butene. y In the third` run, thel eiiiuent from dehydrochlorination was richer in v2,3-dirnethyl-2-butene than Avi/ias thev eiiluent from the othertwo runs prior to the icel water quench, thus ,permitting more back reaction in this run because the hydrogen .chloride'had. to diffuse or bubble through av relatively deep supernatant hydocarbon ylayer before dissolving in the water below. a

I claim: Y

1. A process for producing mono-olenic hy drocarbons which comprises chlorinating '2,3-di-v methylbutane under conditionssuch that monochloride derivativesrofV said hydrocarbon are the. principal reaction products, separating thus produced monochloride derivatives from more highly chlorinated derivatives ofsaid hydrocarbon, separating the primary monochloride derivative from the tertiary monochloride derivative by fractionally distilling the mixture of same at a kettle temperature eiecting concomitant selective dehydrochlorination 'of the .tertiarymonof chloridederivative and distillation of resulting` monofolelnic,hydrocarbons and -hydrogen chlo.

11 ride as overhead product, and removing liquid unconverted primary monochloride derivative as kettle product.

2. A process for producing mono-oleiinic hydrocarbons which comprises chlorinating 2,3-di- .methylbutane with a hydrocarbon to chlorine molar ratio within the range of 4:1 to 10:1, separating thus produced monochloride derivatives from more highly chlorinated derivatives of said hydrocarbon, separating the monochloride derivatives by fractionally distilling the mixture oi same at a kettle temperature effecting concomitant selective dehydrochlorination of the tertiary monochloride derivative and distillation of resulting mono-oleflnic hydrocarbons and hydrogen chloride as overhead product, and removing liquid unconverted primary monochloride derivative as kettle product, and separating from ksaid dehydrochlorination effluent mono-olefinic hydrocarbons.

3. A process for producing tetramethylethylene which comprises chlorinating 2,3-dimethylbutane with a hydrocarbon to chlorine molar ratio within the range of 4:1 to 10:1, separating thus produced monochloride derivatives from more highly chlorinated derivatives of said hydrocarbon. separating the monochloride derivatives by fractionally distilling the mixture oi same at a kettle temperature of at least 120 C. effecting concomitant selective dehvdrochlorination of the tertiary monochloride derivative and distillation of resulting mono-olenic hydrocarbons and hydrogen chloride as overhead product, and removing liquid unconverted primary monochloride derivative as kettle product, introducing an inert diluent lower boiling than the lowest boiling hexene isomer to the dehydrochlorination efliuent thus produced, and separating from said dehydrochlorination efiiuent mono-olefinic hydrocarbons.

4. A process according to claim 3 wherein the chlorination reaction is effected at a temperature of 40 to 55 C. and at hydrocarbon to chlorine molar ratios within the range of 8:1 to 10:1.

5. A process according to claim 3 wherein the dehydrochlorination effluent is separated into its respective components by fractionation in the presence of normal pentane as a diluent.

6. A process for producing tetramethylethylene which comprises chlorinating 2,3-dimethylbutane with a hydrocarbon to chlorine molar 'ratio within the range of 4:1 to 10:1, separating thus produced monochloride derivatives from more highly chlorinated derivatives .of said hvdrocarbon, separating the primary monochloride derivative from the tertiary derivative by fractionation at a kettle temperature of from 120 to 130 C. in the presence of a dehvdrochlorination catalyst so that the primary monochloride derivative is present in the kettle product and the tertiary monochloride derivative is selectively dehydrochlorinated. introducing an inert diluent lower boiling than the lowest boiling hexene isomer to the dehydrochlorination eluent thus produced, and separating from said dehydrochlorination eluent mono-oleiinic hydrocarbons.

7. A process according to claim 6 `wherein the dehydrochlorination catalystis barium chloride.

8. A process for producing mono-olenic hydrocarbons which comprises chlorinating 2,3-dimethylbutane at `a temperature of 40 to 55 C. and a molar ratio of hydrocarbon to chlorine within the range of 4:1 to 10:1, separating thus produced monochloride derivatives from more highly chlorinated derivatives of said hydrocarbon, separating the monochloride derivatives vby fractionally distilling the mixture of same at a kettle temperature of at least C. effecting concomitant selective dehydrochlorination of the tertiary monochloride derivative and distillation of resulting mono-olefinic hydrocarbons and hydrogen chloride asoverhead product, and removing liquid unconverted primary monochloride derivative as kettle product, dehydrochlorinating primary monochloride derivative from said iractional. distillation, and separating mono-oleiinic hydrocarbons produced in the two dehydrochlorination steps.

9. A process for producing tetramethylethylene which comprises chlorinating 2,3-dimethylbutane at a temperature of 40 to 55 C. and a molar ratio of hydrocarbon to chlorine within the range of 4:1 to 10:1, separating thus produced monochloride derivatives from more highly chlorinated derivatives of said hydrocarbon, fractionally distilling said monochloride derivatives at a kettle temperature of 120 to 130 C. to separate the primary monochloride derivative from the tertiary monochloride derivatives and to selectively dehydrochiorinate said tertiary monochloride derivatives, dehydrochlorinating primary monochloride derivative thus separated at a temperature of 500 to 600 C., and recovering tetramethylethylene as a product of the process.

10. A process according to claim 9 wherein the dehydrochlorination of the primary monochloride derivative is effected at a temperature of 500 to 600 C. and in the' presence of a dehydrochlorination catalyst.

11. A process according to claim 10 wherein the dehydrochlorination catalyst is `anhydrous barium chloride.

l2. A process for producing mono-oleiinic hydrocarbons which comprises chlorinating 2,3-dimethylbutane at a temperature of 40 to 55 C. and a molar ratio` of hydrocarbon to chlorine Within the range of 4:1 to 10:1, separating thus produced monochloride derivatives from more highly chlorinated derivatives of said hydrocarbon, fractionally distilling said monochloride derivatives at a kettle temperature of 120 to r130 C. to separate the primary monochloride derivatives from the tertiary monochloride derivatives and to selectively dehydrochlorinate said tertiary monochloride derivatives, dehydrochlorinating primary monochloride derivative thus separated at va temperature of 500 to `600" C., introducing an inert diluent lower boiling than the lowest boiling hexene isomer to the effluents from the dehydrochlorination of the tertiary and primary monochloride derivatives, and separating from said dehydrochlorination eiiiuents mono-oleiinic hydrocarbons.

13. A process for producing tetramethylethylene which comprises chlorinating 2 S-dimethylbutane at a temperature of 40 to 55 C. and a molar ratio of hydrocarbon to chlorine within the range of 4:1 to 10:1, separating thus produced monochloride derivatives from more highly chlorinated derivatives of said hydrocarbon, fraotionally distilling said monochloride derivatives at a kettle temperature of 120 to 130 C. to separate the primary monochloride derivatives from the tertiary monochloride derivatives and to selectively dehydrochlorinate said tertiary monochloride derivatives, dehydrochlorinating primary monochloride derivative thus separated at a temperature of 500 to 600 C. and in the presence of anhydrous barium chloride, introducing an inert diluent lower boiling than the lowest boiling hexene isomer to the efliuents from the dehydrochlorination of the tertiary and primary monochloride derivative, separating from y said dehydrochlorination eiiluents mono-olefinic hydrocarbons, and recovering tetramethylethylene as a product of the process.

14. A process for producing mono-olenic hydrocarbons which comprises chlorinating 2,3-dimethylbutane at a temperature of 40 to 55 C. and a molar ratio of hydrocarbon to chlorine within the range of 4:1 to 10:1, separating thus produced monochloride derivatives from more highly chlorinated derivatives of said hydrocarbon, fractionally dstilling said monochloride derivatives at a kettle temperature ci 120 to 130 C. to separate the primary monochloride derivatives from the tertiary monochloride derivatives and to selectively dehydrochlorinate said tertiary monochloride derivatives, dehydrochlorinating primary monochloride derivative thus separated at a temperature of 500 to 600 C. and in the presence of anhydrous barium chloride, contacting the eiiluents from the dehydrochlorination of the tertiary and primary monochloride derivatives with 1-chloro-2,3dimethylbutane, and separating from said dehydrochlorination effluents mono-olenic hydrocarbons.

15. A process for producing tetramethylethylene which comprises chlorinating 2,3-dimethylbutane at a temperature of 40 to 55 C.- and a molar ratio of hydrocarbon to chlorine Within the range of 4:1 to 10:1, separating thus produced monochloride derivatives from more high- 1y chlorinated derivatives of said hydrocarbon,

fractionally distilling said monochloride derivatives at a kettle temperature of 120 to 130 C. to separate the primary monochloride derivatives from the tertiary monochloride derivatives and to selectively dehydrochlorinate said tertiary monochloride derivatives, dehydrochlorinating primary monochloride derivative thus separated 'at a temperature of 500 to 600 C. and in the presence of anhydrous barium chloride, contacting the effluents from the dehydrochlorination of the tertiary and primary monochloride derivatives with 1-chloro-2,3-dimethy1butane at a temperature of to 50 C. to separate mono-olenic hydrocarbon derivatives of 2,3-dimethylbutane from said eiiiuent, and recovering tetramethylethylene as a product of the process.

DONALD R. BLUMER.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 1,975,456 Hass et al. Oct. 2, 1934 2,065,323 Thomas et al. Dec. 22, 1936 2,278,719 Davis et al. Apr. 7, 1942 2,314,335 Frey Mar. 23, 1943 2,368,446 Buc Jan. 30, 1945 2,404,927 Schmerling et al. July 30, 1946 2,419,500 Peterson et al. Apr. 22, 1947 2,436,491 Schmerling et al. Feb. 24, 1948 2,467,965 Chenicel Apr. 19, 1,949 

1. A PROCESS FOR PRODUCING MONO-OLEFINIC HYDROCARBONS WHICH COMPRISES CHLORINATING 2,3-DIMETHYLBUTANE UNDER CONDITIONS SUCH THAT MONOCHLORIDE DERIVATIVES OF SAID HYDROCARBON ARE THE PRINCIPAL REACTION PRODUCTS, SEPARATING THUS PRODUCED MONOCHLORIDE DERIVATIVES FROM MORE HIGHLY CHLORINATED DERIVATIVES OF SAID HYDROCARBON, SEPARATING THE PRIMARY MONOCHLORIDE DERIVATIVE FROM THE TERTIARY MONOCHLORIDE DERIVATIVE BY FRACTIONALLY DISTILLING THE MIXTURE OF SAME AT A KETTLE TEMPERATURE EFFECTING CONCOMITANT SELECTIVE DEHYDROCHLORINATION OF THE TERTIARY MONOCHLORIDE DERIVATIVE AND DISTILLATION OF RESULTING MONO-OLEFINIC HYDROCARBONS AND HYDROGEN CHLORIDE AS OVERHEAD PRODUCT, AND REMOVING LIQUID UNCONVERTED PRIMARY MONOCHLORIDE DERIVATIVE AS KETTLE PRODUCT. 